Insecticidal compositions containing cyclethrin



United States Patent O INSECTICIDAL COMPOSITIONS CONTAINING CYCLETHRIN Harry L. Haynes, Bronxville, N.Y., assignor to Union Carbide Corporation, a corporation of New York No Drawing. Application November 20, 1953 Serial No. 393,508

13 Claims. (Cl. 167-30) CH GHQ-CH2 3- (2-eyc1opentenyl) -2-methyl-4-oxo-2-cyclopentenyl chrysanthemumate CH=CH This ester and the process of making it, and certain intermediates employed in the process are described and claimed in Guest and Stansbury application Serial No. 363,688, filed June 23, 1953.

One of the largest uses for pyrethrum today is for the control of household pests such as flies, mosquitoes, moths, roaches, silverfish and similar insects. Formulated, for instance in petroleum oil it can be applied as a space spray or applied as an aerosol. In household sprays, for example, a recommended concentrate of pyrethrins (active ingredient of pyrethrum flowers) would contain the extract of twenty pounds of pyrethrum flowers to the gallon of solvent, such as petroleum oil distillate. This concentrate could then be diluted to a pyrethn'n content of about 0.05 to 0.25 percent by weight for a household spray. Because of the high cost of pyrethrins and because the action of pyrethrins tends, at use (levels, toward paralysis rather than outright killing, they are supplemented with rotenone, thiocyanates, DDT and related materials to provide kill. Such mixtures give both kill and knockdown.

Until the synthesis of allethrin in the laboratories of the Department of Agriculture, pyrethrum was unique in its rapid paralytic properties and freedom from hazard to mammalian organisms and the only material of its type which could be used to provide rapid knockdown (paralysis) of flies. Two of the active constituents of pyrethrum flowers are esters of substituted 3-'methyl-2- cyclopenten-4-ol-1-ones and chrysanthemummonocarboxylic acid. In the procedure employed-for the synthesis of allethrin, chrysanthemummonocarboxylic acid and 2- allyl-3-methyl-2-cyc1openten-4-ol-l-one are each prepared separately by a series of steps, followed by the formation of the ester from these two components. The following schematic equation is illustrative of the last step which is the formation of the ester:

(oH3),o=oHoEo(oH CH -OO ohooljqiijii ohn omon on,

CGH Ohrysanthemum- 2-allyl-3-methyl-2 cyclomonocarboxylic acid pentent-ol-l-one 2,891,889 Patented June 23, 1959 OCH;

The application to this alcohol and this acid of conventional procedures for forming an ester, involving as they do elevated temperatures and long reaction periods, results in deterioration of the cyclopentenolone molecule and poor yields of allethrin. The process suggested by La Forge and others (J. Org. Chem, vol. 12, pp. 199-202 (1947); J. Chem. Soc. (1950), pp- 3552-63) employs the acid chloride made by the action of thionyl chloride upon the acid. The acid chloride in turn is reacted with the cyclopentenolone in the presence of pyridine to give allethrin. A number of difficulties over and above those arising out of the corrosive nature of the thionyl chloride and the noxious qualities of the sulfur dioxide and hydrogen chloride evolved are encountered in this final step of making allethrin. For instance, certain coproduct al cohol impurities present in the 2-al-lyl-3-methyl-2-cyclopenten-4-ol-1-one are also esterified by the acid chloride treatment. The resulting ester impurities in the allethrin are of low insecticidal activity and very difiicult to remove from the allethrin. In addition, sulfur and chlorine 1 compounds of unknown structure are formed and remain 1 which is represented for use as a safe insecticide.

The difficulties and shortcomings of the acid chloride procedure have been obviated by the use of chrysanthemummonocarboxylic acid anhydride in the esterification Serial No. 299,729, filed July 18, 1952, now United States Patent No. 2,768,965, issued October 30, 1956.

By reach of the numerous steps required for the synthesis of chrysanth emummonocarboxylic acid and 2-allyl- 3-methyl-2-cyclopenten-4-ol-l-one, and also the complicated nature of the operations, allethrin is and is likely to remain a high cost chemical for use in householdtype oil sprays. Currently, the price of allethrin is about three-fifths the price of pyrethrins. Pyrethrins and allethrin, by themselves, in household-type oil sprays are capable of kill, as well as knockdown of insects, such as flies and roaches, if used in sufiicient amount. From a practical, economic viewpoint, this is too expensive. Although the annoyance from flies is removed for a time when they are no longer capable of flight, an amount of pyrethrins or allethrin sufiicient to provide knockdown is not sufi'icient to kill. With roaches also, an amount of pyrethrins or allethrin insufiicient to kill is insufficient to activate them so that they will come out into the open where they can be sprayed directly with chemical for a kill. To bring down the cost of the sprays, they have to be fortified either with another toxicant or killing agent, such as DDT or methoxychlor, for instance, or with a synergist to extend or broaden their action or both.

The scarcity of pyrethrum during World War II stimulated the search for and development of addition materials which would improve the efficiency of the pyrethrins. To these addition materials which, of themselves, have little or no value as insecticides, the terms activators, extenders, and synergists have variously been applied. One of the earliest synergists developed for pyrethrins is N-isobutylundecylenamide introduced about 1938. Sesame oil of which the active ingredient, sesemin, was found to be a synergist for pyrethrins, was discovered (US. Patent 2,202,145; 1940) at about this i same time. The knowledge acquired about the structure of sesemin led to the synthesis of related compounds such as piperonyl butoxide, piperonyl cyclonene, npropylisome, and sulfoxide, which are the most commonly used pyrethrin synergists. Other less effective synergists are N-(Z-ethylhexyl)-bicycloheptenedicarboxamide, the pinene ether of ethylene glycol, and a polyoxypropylene glycol monobutyl ether having a viscosity between 100 and 850 Saybolt Universal seconds at 100 F.

As in the case of pyrethrum, efforts have been made to extend the insecticidal usefulness of allethrin. Although allethrin currently is not as costly as pyrethrurn, on the other hand it is not capable of being as highly activated or synergized by the available pyrethrum synergists, as is pyrethrum.

My activated or synergized compositions containing cyclethrin are more effective than are prior compositions containing other pyrethrum replacements, as evaluated by standard tests against household pests, for instance. They are more effective also against ectoparasites of animals. In addition, my synergized compositions can be used to protect food products such as wheat and corn from insect attack. The number of chemicals available for this use is quite limited because of the dangers from residues left in the final food product consumed by humans and other animals. Because of the freedom of cyclethrin from mammalian toxicity, compositions in which it is the essential insecticidal ingredient can be used to advantage for these purposes.

The synthesis of cyclethrin involves a number of steps, the reactions of which can be illustrated by the following scheme of equations:

STEP 1 Hydrogen chloride is caused to add to cyclopentadiene which is a relatively inexpensive starting material to form 2-cyclopentenyl chloride C H=C H C H: C H

C H H 01 O H 01 C H -O H O H: C H; cyclopentadiene hydrogen Z-cyclopentenyl chloride chloride STEP 2 2-cyclopentenylacetone is formed by the reaction of sodium acetoacetic ester with the 2-cyclopentenyl chloride from Step 1, followed by ketonic cleavage.

Ethyl 4-(2-cyclopentenyl)-3-ketobutyrate is made by reaction of diethyl carbonate with the 2-cyclopenteny1 acetone product of Step 2.

2-cy010pentenyl acetone diethyl carbonate H2O H O HOH C O CH ii O O H CH -(3H ethyl 4(cyclopentenyl) -3- ketobutyrate 4% STEP 4 Pyruvie aldehyde is reacted with the ethyl 4-(2-cyclopentenyl)-3-ketobutyrate product of Step 3 in the presence of dilute aqueous alkali metal hydroxide to form 6 (2 cyclopentenyl)-3-hydroxyhexane-2,S-dione. The ester is saponified to the sodium or potassium salt of the corresponding acid, which salt in turn condenses with the pyruvic aldehyde.

(3 H: O H O i JHCHZCOCHZ +HOCOCH H G H; H 4-(2-cyclopentenyD-3- pyruvic ketobutyric acid aldehyde CH=GH l i3HCH C-OH OHOHCCH CO CH,O H I 1 6- (Z-cyclopentenyl) -3-hydroxyhexane-2, 5- dione STEP 5 The product of Step 4 is treated with dilute sodium hydroxide to form 2-(2-cyclopentenyl)3-methyl-2-cyclopenten-4-ol-1-one.

H 0 0- 013 CH CH COH OH =(lJH I JH'CH l GEL-(3(2) (UCHOH ta CHCH O=(|3-CHOH CH3 H OCH;

CH; 6- (Z-cyclopentenyl) -3-hydroxy- 2- (2-cyc1o pentenyl-3-methylhexane-2,5-dione 2eyclopenten-4-ol-1one STEP 6 Finally, the cyclopentenolone product of Step 5 is treated to form the ester of dl-cis and dl-trans chrysanthemummonocarboxylic acid preferably through the anhycyclethrin Cyclethrin is a mixture of isomers, including four racemic forms or eight optical and geometric isomers. These isomers have not yet been isolated and evaluated.

While it might be possible, on the basis of a graphic representation of structure, to regard this new ester as similar to allethrin except for a 2-cyclopentenyl group in a position corresponding to that occupied by an allyl group in allethrin, such a view would be an oversimplification, unwarranted by the facts. Even were it possible to employ allethrin as a starting material for the preparation therefrom of other compounds by the direct substitution of the allyl group, it does not follow that all of the products would exhibit the same useful biological activity. For instance, according to my studies and information, the following esters of chrysanthemummono- 'carboxylic acid are inferior in insecticidal activity or value:

$11,. C H3 0 L UH OHgC OHOchrysanthemumyl 3-methal1yl-2-methy14-oxo-2-cyclopenteny1 chrysanthemumate 3- (3-cyclohexeny1methyl) -2-methyl-4-oxo-2-cyc1opentenyl chrysanthernumate C OCH,

CHFCHCH2C\ CH-O CH OH O CH C fi O-chrysanthemumyl O OH;

6- ('3-allyl-2-methyl-4-oxo-2-cyclopentenyl) -3,6-dioxahexyl chrysanthemumate C.O-OH1 on=orrorno on-o OH CH O-chrysanthemumyl Com 3- (3-a1Iy1-2-methylkoxo-2-cyclopenteny1)3-oxapropyl chrysanthemumate Biological testing of cyclethrin, unsynergized, reveals that it is of the same order of effectiveness as furethrin (.3 furfuryl-Z-methyl-4-oxo-2-cyclopentenyl chrysanthemummonocarboxylate), unsynergized; and that both are equal to allethrin, all unsynergized. It reveals also that those synergists which are superior in effectiveness with pyrethrin can also be used as synergists for cyclethrin. In general, slightly higher knockdown is obtainable with synergized pyrethrin than with cyclethrin synergized with the same synergists.

However, when synergized cyclethrin is compared with synergized allethrin only one-half as much cyclethrin is required with Sulfoxide or with n-propyl isome; only one-third as much cyclethrin with piperonyl butoxide and. only one-half to two-thirds as much with sesame oil extractives.

Another advantage of my new composition is that the effective insecticidal ingredient therein, cyclethrin, is even less toxic to mammals on a direct concentration basis than is allethn'n. According to one set of tests, undiluted cyclethrin (95.6 percent purity) has an LD-SO for rats in the neighborhood of 1.4 grams per kilogram as compared with 0.34 gram per kilogram for allethrin. According to another set of tests, the LD-SO for cyclethrin fedto male albino rats by intubation is 1.78 grams. per kilogram. Fed as a dilution in Bayol D, the toxicity of cyclethrin is much less. For instance, at a concentration of 1 0 percent by weight in Bayol D, 3.98 grams per kilogram of cyclethrin killed only one of five rats while 2.0 and 1.0" gram per kilogram has allowed survial. Similarly, at a concentration of 20 percent by weight in Bayol D, the LD-SO for fnale albino rats is 4.9 grams per kilogram on the basis of the active ingredient.

For comparison, the LD-SO dose for diluted allethrin fill M l. fill per kilogram and at a 20 percent concentration by weight in deodorized kerosene it is 0.92 gram per kilogram for male rats. According to these studies, cyclethrin seems to be of the order of about one-fifth as toxic as allethrin for rats in single oral doses on a direct concentration basis, and still less at actual use levels.

Compounds which are useful in my composition as synergists in combination with cyclethrin are:

A. Piperonyl butoxide which is a technical grade of the 3,4-methylenedioxy-6-propylbenzyl ether of diethylene glycol monob utyl ether having a structure as. represented by the following graphic formula:

CH O (321140 02114 A Q CHTJ) Compounds closely relate to the above amount to about 20 percent by weight of the piperonyl butoxide.

B. Normal-propyl isome which is the name given to di-n-propyl-2-methyl-6,7-methylenedioxy-l,2,3,4 hexahydronaphthalene-3,4-dica1'boxylate. Its structure can be represented by the following graphic formula:

CHCH H,0

F onooooanv C. Synergist 6266 which is the number assigned to N- (hexoxyethoxypropyl) -bicyclo- [2.2.11-5-heptene 2,3 dicarboximide having a structure as represented by the following graphic formula:

' CH-CHCH-C=O u +Hg i NCHaOC'2H40Ca 13 OH-OH HC=O D. Sulfoxide which is the name given to the n-octylsulfoxide of isosaphrole. It has a structure Which can be graphically represented as follows:

s iv E. N-isobutyl undecylene amide, having the general formula CH =CH(CH CONHC H F. Pinene ether of ethylene glycol, having the empirical formula C H OCH CH OH G. Piperonyl cyclonene, which is a mixture of 3-isoamyl-5-(3,4 methylene dioxyphenyl) 2 cyclohexenone and its 6-carbethoxy derivative 3-is0an1yl-5- (3,4-methylene dioxyphenyl) -2-cyclohexenone H. Polyoxypropylene glycol monobutyl ether having a viscosity of between and 850 Saybolt Universal seconds (S.U.S.) at 100 F. A typical polyoxypropylene glycol monobutyl ether which is suitable for use on animals, humans, and plants has the following characteristic properties: average molecular weight, about 800;

S.U.S. at 100 F., about 250; average number of oxypropylene groups, 3 (est.) flash ,point,, approximately 7 420 F.; specific gravity (20/20 C.), 0.990; known commercially as Crag brand fly repellent.

I. Sulfone, which is the name given to normal octylsulfone of isosaphrole.

I CH OGnHiMOFaH.

J. Synergist 264 which is the number assigned to N-(2- ethylhexyl bicyclo [2.2.1] -5-heptene-2,3-dicarboximide.

HO CH-CO K. Sesame oil is the name given to the oil from sesemum indicium of which about 0.25 percent is sesemin. The structure of sesemin can be represented graphically by the formula:

Of the eleven synergists named, sulfoxide and piperonyl butoxide are preferred.

Cyclethrin concentrates, containing in addition to cyclethrin other biologically active materials such as, for instance, a polyoxypropylene glycol monobutyl ether (Crag brand fly repellent); beta-butoxy-beta-thiocyanodiethyl ether and a mixture of the beta-thiocyanoethyl esters of higher fatty acid having to 18 carbon atoms (known commercially as Lethanes); terpene thiocyanoacetates (known as Thanite-Isobornyl Acetate); methoxyohlor; and a synergist can be used to protect live-stock from such ectoparasites as flies, lice and ticks. Illustrative of such a concentrate would be a formulation containing the ingredients in the following relative proportions by weight.

This formulation can be applied directly to cows, for example, in an amount which is from 0.5 to 10 grams per animal per day. If desired, the concentrate can be diluted with water usually in such proportion that the diluted concentrate, so called, can be sprayed in an amount from one to four pints per animal per week to protect against fly attack.

Furthermore, a concentrate as of the above formulation, either with or without emulsifier, can be diluted with petroleum distillate or water and be applied as space sprays for knockdown and kill of flies, moths and the like; or it can be applied to agricultural crops to protect against insect attack. Specifically, beans, corn, cabbage, apples and apple trees, grapes and the likecan be protected from worms, beetles, aphids and spiders. Similarly, it can be sprayed on such surfaces as the interior of grain bins or elevators to kill insects attacking cereal grains, or it can be applied directly on cows or other livestock to protect against fly attack. Still further, these same concentrates when diluted either with oil or water can be applied to such packaged goods as cereals or flour in cloth or paper containers to protect against insect pence tration and infestation. Good results have been obtained with cyclethrin concentrates having the following com.- positions: 1

Polyoxypropylene glycol monobutyl ether; aver. molecular weight about 800.

Cyclethn'n with synergists and a propellant can also be used in aerosols or pressurized sprays to kill insects such as flies, moths, mosquitoes, bedbugs, ants, roaches, confused flour beetles, Silverfish, and the like. Such an aerosol or pressurized spray can contain in addition one or more of the halogenated toxicants such as DDT, methoxychlor or Strobane, for instance, or thiocyanates or thiocyanoacetates and either with or without a solvent such as methylated naphthalenes, petroleum distillates and the like, if desired. Illustrative of a suitable aerosol or pressurized spray is the following formulation:

Pressurized spray Parts by weight Cyclethrin 0.01 to 6.0 Synergist 0.05 to 10.0 Toxicant 1 0.0 to 6.0 Polypropylene glycol monobutyl ether 0.0 to 55.0

Solvent, propellant 3 to make a total of 100 parts by weight of spray.

1DDT; methoxychlor; Strobane; thiocyanates; thiocyanacetates.

Viscosity at 100 C., 250 S.U.S.; av. mol. wt. 800.

3 Freon 11; Freon 12.

My new compositions include also dry formulations of cyclethrin in combination with inert dust-type carriers such as wheat flour, kaolin, talc, pyrophyllite, diatomaceous earth, kieselguhr, bentonite, ground walnut hulls, ground sawdust and the like. These dry formulations are especially adapted for protection of cereal grains and flour against insect infestation. They can also be applied to plant foliage to kill insects or prevent them from feeding. Illustrative of a suitable composition for this purpose is a formulation as follows:

Grain protestant Parts by weight cyclethrin 0.02 to 0.5 Synergist a- 1.0 to 5.0 Inert dust-type carrier, remainder to make 100 parts.

Total The following examples are illustrative.

EXAMPLE 1 pressure of 100 millimeters of mercury. The yield Was;

percent of theory.

[1 moi) [ii iilill iiiiiliiiiiii Will iiliilll 011 1 i l t 1101i of 30 minutes. The mixture was maintained at a temperature of 20 C. during the addition. After the mixture had been stirred for an additional period of one hour at 20 C., it was heated to a temperature of 50 C. and 459 grams of 2-cyclopentenyl chloride (4.5 mols) were added over a period of 1.5- hours. To complete the reaction, the mixture was maintained at its refluxing temperature at atmospheric pressure for a period of 3 hours.

At the end of this time ethanol was removed from the mixture by distillation at atmospheric pressure to a kettle temperature of 125 C. The residue, which contained ethyl 2-cyclopentenyl-acetoacetate, was cooled to 20 C. and 2500 grams of aqueous sodium hydroxide percent; 6.25 mols) were added over a period of30 minutes. To complete the ketonic cleavage of the compound the mixture was stirred for a period of 4 hours while the temperature was maintained at 20 C. Next, 400 milliliters of aqueous sulfuric acid (50 percent) was added to reduce the pH of the mixture to 3.5. The mixture was treated with 200 milliliters of benzene and a distillation carried out at atmospheric pressure using a rectifying column fitted with a decanter of 175 milliliters capacity filled with benzene. During the distillation, a total of one liter of water was fed gradually into the vapor line just before the condenser. The lower layer in the decanter was continually removed while the oil in the decanter was returned as refiux to the still. This procedure was continued until the head temperature reached 68 C. with the result that all of the ethanol was removed from the system while all the Z-cyclopentenylacetone product remained in the still.

Upon distillation of the oil in the residue, to which was added the oil in the decanter, there was obtained 440 grams of 2-cyclopentenyl acetone having the following properties: boiling range at an absolute pressure of millimeters of mercury, 66 C. to 68 C.; specific gravity (/20), 0940. Analysis of the distilled product for ethyl acetoacetate by the sodium methoxide procedure gave a value of 8.3 percent by weight. Analysis for ketone by the hydroxylamine procedure gave a cyclopentenyl acetone content of 89.1 percent by weight after-correction for the ethyl acetoacetate content. Because the boiling points of 2-cyclopentenyl acetone and ethyl acetoacetate lie very close, separation of the two compounds by fractional distillation is not readily accomplished. Upon removal of the ethyl acetoacetate from the 2-cyclopentenyl acetone, by saponification, the pure ketone had a specific gravity (20/20) of 0.934 and a refractive index (11 of 1.4543. The yield of 2-cyclopentenyl acetone was 72 percent based on the 2-cyclopentenyl chloride, correpondirrg to an efliciency of 72 percent.

Part (c).Diethyl carbonate (2240 grams; l9 mols) was charged to a distillation kettle fitted with a refluxing condenser, and heated'under a reduced pressure of 100 millimeters of mercury absolute at its refiuxive temperature. Sodium ethoxide (185.6 grams; 2.73 mole) in the form of a 19.3 percent solution in ethanol (776.4 grams) was fed into the kettle over a period of 2 hours while ethanol was being continually distilled. The total distillate collected was 1033 grams. After all the ethanol solvent had been removed, leaving a suspension of sodium ethoxide in the diethyl carbonate in the still kettle, 340 grams of 2-cyclopentenyl acetone (purity, 91.7 percent; 2.51 mols) were fed over a period of two hours while the distillation was continued as before to remove ethanol. The total amount of distillate removed in this step was 289 grams. The residue was then cooled to C., acetic acid (174 grams; 2.9 mols) added, which was followed by the addition of 620 milliliters of water to dissolve the sodium acetate. The oil layer was separated and distilled rapidly under reduced pressure. There was obtained 400 grams of ethyl 4-(2-cyclopentenyl)-3-ketobutyrate having 10 a boiling range of 100 C. to 155 C. at an absolute pressure of 5 millimeters of mercury. By titration with sodium methylate in pyridine the purity was found to be 94.0 mitt tlllltitti 16121011281101 (time) showed that it contained 82.4 grams of product. The yield based on the 2-cyclopentenyl acetone was percent.

Part (d ).Eight hundred nineteen grams of ethyl 4-(2- cyclopentenyl)-3-ketobutyrate, having a purity of 93.1 percent (3.89 mols) were added dropwise over aperiod of one hour to 2180 grams of a well-stirred aqueous solu: tion of sodium hydroxide (9.5 percent; 5.18 mols) maintained at a temperature of 20 C. to 25 C. At the end of 16 hours, the solution was neutralized to a pH of 7.5 with carbon dioxide.

Fifteen hundred grams of an aqueous solution of pyruvic aldehyde (22.4 percent; 4.67 mols) which had been neutralized to a pH of 7 with 26 grams of sodium hicarbonate was fed to the neutralized solution of the betaketo acid over a period of 1.25 hours while the reaction mixture was maintained at a temperature of 25 C. To complete the reaction, the mixture was allowed to stand 21 hours and then extracted four times with successive l-liter portions of diisopropyl ether. The four extracts were combined and stripped of volatile material to a kettle temperature of C. under a reduced pressure of 4 millimeters of mercury, absolute. There was obtained as a residue product 742 grams of 6-(2-cyclopentenyl)-3- hydroxyhexane-2,5-dione which was found by analysis to have a purity of 75.8 percent. The yield was 74 percent based on the ethyl 4-(2-cyclopentenyl)-3-keto-butyrate.

Part (e).Three hundred sixty-eight grams of 6-(2- cyclopentenyl)-3-hydroxyhexane-2,5-dione having a purity of 75 .8 percent (1.42 mols) was fed dropwise over a period of 30 minutes to 3312 grams of a 2 percent aqueous sodium hydroxide, vigorously stirred and maintained at a temperature of 20 C. to 25 C. After a period of 4 hours allowed for completion of the reaction, the mixture was saturated with sodium chloride and four successive extractions were made, each with one-liter portions of diisopropyl ether. The four extracts were combined, neutralized with 2 grams of acetic acid and distilled under reduced pressure. There was obtained 139 grams of a product fraction which distilled from a temperature of C. at an absolute pressure of 2.5 millimeters of mercury to a temperature of C. at an absolute pressure of 5 millimeters of mercury. This product was found by analysis to contain 72.8 percent of 2-(2-cyclopentenyl) 3-methyl-2-cyclopenten-4-ol-l-one. The yield was 40 percent.

Part (f).-A mixture was formed of 275 grams of 2-(2-cyclopenten)-4-ol-1-one (purity 70.8 percent; 1.094.

mols), 156 grams of pyridine and 0.905 liter of ethanol. To this mixture was added a solution of 183 grams of semicarbazide hydrochloride (1.64 mols) in 220 milliliters of water. The mixture was allowed to stand 16 hours and at the end of that time the crystalsof the semicarbazone which had formed were filtered and washer with 4 liters of water. to remove chloride. Upon crystallizing the semicarbazone from ethanol, 181 grams of colorless crystals having a melting point of 208 C. to 210 C. Were obtained. The yield of the pure semicarbazone of 2-(2-cyclopentenyl) -3-methyl-2-cyclopenten- 4-ol-1-one was 71 percent.

A mixture of 181 grams of the pure semicarbazo'ne tion. Upon distillation of the ether solution there was obtained 101 grams of 2-(2-cyclopentenyl)-3-methyl-2- cyclopenten-4-ol-1-one characterized by the following properties: boiling point at an absolute pressure of 1 millimeter of mercury, 131 C.; refractive index (n 1.5350; purity (by analyses for hydroxyl content), 96.7 percent. The yield based on the semicarbazone was 84 percent, with credit being taken for 17 grams of product contained in the mid-fraction and column holdup.

Part (g).A mixture of 92 grams of 2-(2-cyclopentenyl-3-methyl-2-cyclopenten-4 ol 1 one having a purity of 96.7 percent (0.5 mol), 168 grams of chrysanthemummonocarboxylic anhydride having a purity of 94.8 percent (0.5 mol) and 119 grams of dry butyl ether was refluxed at a temperature of 165 C. for a period of 4 hours. The solution was diluted with 42 grams of butyl ether and washed successively with 263 grams of 7.6 percent aqueous sodium hydroxide (0.5 mol), 0.25 liter of 2 percent aqueous sodium hydroxide (0.125 mol) and 0.25 liter of Water. The washes were each extracted in sequence with a single 0.1 liter portion of dibutyl ether to minimize loss of product. The washed oil and extract were combined, stripped of volatile material at a kettle end temperature of 80 C. at a reduced pressure of 5 millimeters of mercury, absolute, and thereafter stripped with steam. There was obtained 162 grams of residue product characterized by the following properties: refractive index, (n 1.5120; specific gravity (20/20 C.), 1.033; purity by the ethylene diarnine method, 87.1 percent; acid content, as chrysanthemummonocarboxylic acid, 0.1 percent; and chrysanthemummonocarboxylic anhydride content, 0.2 percent. The yield based on the reactants was 88 percent, with credit being taken for 4.3 grams of product consumed in analysis of the reaction mixture for anhydride content.

A number of formulations were prepared in which cyclethrin prepared according to a procedure the same as or similar to those described in Example 1 was tested for eflicacy in admixture with a variety of compounds having a synergistic effect. These formulations were tested by the Poet-Grady Method (Ofiicial Method of the Chemical Specialties Manufacturers Association). The results of these tests together with the comparison test results obtained with the Oflicial Test Insecticide (herein referred to as OTI) and with allethrin formulations similarly synergized are given in the following examples:

EXAMPLE 3 Formulation A B OTI cyelethrin, milligrams allethrin, milligrams... 50 pyrethrins, milligrams... 100 n-oetyl sulfoxide of isosafrole, milligrams... 250 250 deodorized kerosene traction, milliliters 100 100 100 Large group Peer-Grady results Percent OTI Difierence N o. of Percent Knock- Formulation Tests down,

24 Hrs. 10 min. Kill Knockdown These test results show that the plus values for kill and knockdown of the synergized cyclethrin compared with OTI are better by 38 and 5.9 percentage points, respectively, than a similar comparison of synergized allethrin with OTI.

EXAMPLE 4 Formulation A B OTI eyelethrin, milligrams. allethrin, milligrams... 42 pyrethrins, milligrams. 100 npropyl isome, milligrams.. 600 deodorized kerosene fraction, milliliters 100 100 100 By n-propyl isome is meant (di-n-pr0pyl-2-methyl-6,7-methylene' The results of this test show that the plus value for kill for synergized cyclethrin compared with OTI is better by 18 percentage points than a similar comparison of synergized allethrin with OTI; while the knockdown is EXAMPLE 2 50 only slightly less favorable by 1.9 percentage point. Formulation A B OTI EXAMPLE 5 cy l l r milligrams 25 Formulation A B OTI allethrin, milligrams..- 25 pyrethrins, milligrams 100 piperonly butoxide, milligrams 200 200 cyelethrin, milligrams 40 deodorized kerosene fraction, milliliters 100 100 100 allethrin, milligrams 40 pyrethrins, milligrams 100 sesame oil, milligrams 150 150 deodorized kerosene fraction, milliliters 100 100 100 Large group Peer-Grady results Lar e grou Peer-Grad results P \I f P ffgercefit OTI Difierence l 0.0 ercent noe Formulation Tests Kill, down, N f t -2 OTI Difference 24 Hrs 10 min. Kill Knock- F 0 P 00 down ormulation Tests Kill, down,

24 Hrs. 10 min. Kill Knock- 5 down A. egielelthrin... 5 61.3 91.2 +25 2.8 6 B. a at I'm 5 40.0 90.0 +4 -4.0

A. cyclethrin 3 26.1 89.8 -11 -64; OTI 8 9M B, allethrin.. 3 18.8 90.8 -18 -s.4

OTI 5 37.4 96.2

The results of this test show that the value for kill of,

These test results show that the plus value for kill and the minus value for knockdown of the synergized cyclethrin compared with OTI are better by 21 and 1.2 percentage points, respectively, than a similar comparison of synergized allethrin with OTI.

the sesame oil-synergized cyclethrin, even though minus l compared with OTI, is better by +7 percentage points than a similar comparison of synergized allethrin with OTI; while the knockdown is only slightly less favorable by1 percentage point. 3

Chemical identification: N-(hyxoxyethoxypr'opyl)bicycle-[22.1115- 10 heptene-2,-3-dicarboxlmide.

Ilarg'e group Peat-Grady results Percent OTI Difference- No.01 Percent Knockl5 Formulation Tests down,

24 Hrs. min. Kill Knockdown A. clethrin 5 46.6 94.2 +13 +0.2 Bg'aleth' 5 31.4 92.1 -3 1.9 OTL'. 8 34.3 94.0

results of this test show that the plus values for kill and knockdown of the synergiz'ed cyclethrin, compared with OTI, are better by 16 and 2.1 percentage points, respectively, than a similar comparison of synergized allethrin with OTI.

EXAMPLE 7 Formulation A B' elethriu' milli ams 51 31 mm; inmm a mq 51 py-rethflns; milli rams synergist 264, milligrams 1, 000 1,000 deodorized kerosene'iraetion, milliliters 100 100' Ohemical identification: N-(2-ethylhexyl)-bicycl0-[2.2.1]-5-heptene- 2,3 dicarboximide.

Large group Feet-Grady results Percent OTI Difference No. of Percent Knock- Formulation Tests down, 7

24 Hrs. 10 min. Kill Knockdown A. cyclethrin 31 .8 93.0 7 --1.5 B. aliethrim- 5 29.0 90.7 +4 3.8 0T1 24.9 94. 5

According to these tests, the Oflicial Test Insecticide (OTI) is only 1.5 percentage points better than synergized cyclethrin for knockdown, as compared with 3.8 percentage points better than synergized allethrin, a superiority of 2.3 percentage points in favor of cyclethrin overallethrin for knockdown.

EXAMPLE 8 Tests were carried out on a formulation containing cyclethrin as an oil-base livestock spray in comparison with a commercial oil-base livestock spray containing pyrethrins. Theproportion of ingredients present in the formulation was as follows:

Formulation A B O eyclethrin, milligrams. 15 pyrethrins milligrams 25 15 plperonyl but'oxide, milligrams 200 120 120 polyoxypropylene glycol monobutyl ether- 5 5 Spray oil added to make up solutions to a volume of 100 milliliters.

and the sprays were applied at intervals ofthree to four 14 days at a rate of two ounces per animal. ites rays' were applied in mid-afternoon and counts. were; taken at noon on the following day, of horn flies =h) stable flies (=5); anti house flies (=H). The ratio of the fly I I t speciesm total population war All! tlidill, respectively, for hornflies, stable flies and'house flies.

The results of these tests in terms of repellency are given in the following table:

Percent Repellency at- Repel- Fly lenoy for Species Period,

24 hr. 48 hr. 72 hr. Average 65. 7 55. 4 31. 8 50. 9 44. 4 41. 7 3.0 29. 7 Spray A (pyrethrins) 50. 9 41. 2 21. 5 37. 9 40.0 35. 3' 43. 1 39. 5 90.0 76. 8 47. 8 71. 5 71. 5 63.8 50. 2 61.8 49.- 7 50. 0 27. 7 42. 5 Spray B- (pyrethrins) 71. 1 35. 8 40. 5 49.1 57. 3 44. 5 48. 8 50. 2 88.0 88. 1 74. 6 81. 6 74. 2 63.0 52. 0 63. 1 60. 0 43. 0 0 34. 7 Spray 0 (cyclethrin) 74. 9 47. 1 52. 3 58. 1 65. 2 41. 4 55. 5 54.0 84. 7 88. G 93. 7 89. 0

The above values for percentage repellency is based on the number of counts taken, as follows:

Fly Species 24 hrs. 7 48 hrs. 72 hrs.

According to these tests, the synergizedcyclethrin formulation as an oil-base livestock spray is shown to be more effective in repellency against horn, stable and house flies than commercial formulations of synerg-ized' pyrethrins. It is to be noted that Spray C is superior to Spray B, and at the same time cheaper than Spray B and, accordingly, Spray A. Thus, at current prices for the ingredients of the respective formulations, this in: creased effectiveness with synergized cyclethrin is obtal'nable without increase in cost.

EXAMPLE 9 Formulation OTI A B O piperonyl butoxide, milligrams 120 pyrethrins, milligrams l5 Crag Fly Repellent, milliliters 5 5 oyclethrin, milli r m 15 deodorized kerosene to make 100 milliliters of solution.

1 Polyoxypropyl'ene' glycol monobutyl ether.

Large group Feet-Grady test results for control of flies Percent Knockdown Percent OTI Dif- Formulation No. of Kill, 24 ference Tests Hours and Rat- 3 min. 5 min. 10 min. ing

6 86.1 90. 2 95. 2 67.9 +31 AA 6 87. 0 92. 6 96.0 7 2. 3 +86 AA 6 80.8 85. 4 93. 6 70. 3 +34 AA 10 91. 5 93. 9 94.9 36. 7 -B According to these tests, Spray C is eifectivezin' ten-x 1.5 minute knockdown and kill as Spray B, while at the same time it is less expensive.

EXAMPLE 10 The eflicacy against the German roach was determined for cyclethrin alone, and for cyclethrin in combination with sulfoxide (n-octyl sulfoxide of isosafrole) as synergist. The tests were carried out by immersing roaches in an emulsion of the cyclethrin for a period of 10 to 15 seconds. Ten roaches were employed in each test, and comparison tests made employing allethrin. Dosage series tests were conducted and the results plotted on a logarithmic probability scale. The formulation and dosages tested are shown in the following table:

Formulation, Series 1 Formulation 1 Oyclethrin,

Milligrams Allethrin, Milligrams Sulfoxide, Milligrams 1 In addition, each of the solutions contained 0.02 milliliter of Triton; 5 milliliters of acetone, and the whole made up with water to a total volume of 0.1 liter.

The results in terms of the dosage required for 50 percent of the roaches to be killed within 24 hours (LD- 50) by the to second immersion are given in the following table:

Results, Series 1 Results, Series 2 Milligrams Formulation for kill LD-50, 24 hours A through E (cyclethrin) 15 F through E (cyclethrin) .s 4. 5 I through M (allethrin) 3 N through P (allethrin) M 2.7

In both series, cyclethrin Was synergized more effectively than allethrin. In the case of allethrin, only onehalf or less of the amount required unsynergized Was saved by synergizing it, whereas in the case of cyclethrin it was possible to save from two-thirds to four-fifths of the amount required unsynergized.

EXAMPLE 11 The eflicacy against the bean aphid on nasturtiuni plants was determined for cyclethrin, alone, and cyclethrin synergized with sulfoxide (n-octyl sulfoxide of isosafrole), and synergist 6266 (N-(hexoxyethoxypropyl) bi-cyclo- [2.2. l -5-heptane-2,3 -dicarboximide) Similar tests were also made with allethrin.

Allethrin, Oyclethrin, Sulfoxide, Synergist.

llormulation milligrams milligrams milligrams 6266, milll grams Milligrams for kill Within 24 hours (LD-) Formulation A through D (cyclethrin). H through K (allethrin) E through G (cyclethrin). L through N (allethrin) A second series of tests were run in the same manner using the formulations and dosages shown in the following table:

F ormulazvion, Series 2 Allethrin, Milligrams Sulioxide, Milligrams Formulation 1 Cyclethrin,

Milligrams 1 In addition, each of the solutions contained 0.02 milliliter of Triton 5 milliliters of acetone, and the Whole made up with water to a tota volume of 0.1 liter.

The results in terms of the dosage required to kill 50 percent of the roaches in 24 hours are given in the fol,- lowing table:

In addition, each of the formulations contained 10 millimeters of acetone, an amount of emulsifier which was 10 percent of the total weight of toxicant (allethrin or cyclethrin, plus synergist when used), and water in an amount such as to make a total volume of 0.1 liter.

The resulting mixture was agitated and sprayed on potted nasturtium plants, each pot of plants being infected with approximately 250 nymph and adult bean aphids. Potted plants were set on a revolving turn-table and milliliters of the 100 milliliters of the formulation were applied from a De Vilbiss sprayer, model CH-62041, under a pressure of 40 pounds per square inch. Counts of dead aphids were taken twenty-four hours after treatment was applied. Dosage series tests were conducted and the results plotted on a log probability scale. The results in terms of the LD-50 and the LD- for a 24-hour kill were as follows:

Milligrams for kill Within 24 hours Formulation LD-50 LD-95 A through E (allethrin) 10 70 F through E (allethrin) 10 20 v I through M (cyclethrin) 10 80 N through P (cyclethrin)- l 11 Q through S (allethrin) 6 14 '1 through V (cyclethrin) 2 12 W through Y (allethrin) 5 13 Z through BB (eyclethrin) 3 9. 5

According to the results of these tests, cyclethrin is rendered more 'eflfective by the synergists than is allethrm, by a considerable factor.

EXAMPLE 12 A comparison was made of cyclethrin and allethrin against houseflies in large group Peet-Grady tests. The results, which are the average of five tests are given in the following table:

In milligrams per 100 milliliters of solution in deodorizod kerosene fraction.

An analysis of the variance of the above results shows 1,000) 'BZ (cyclethrin, 30; synergist Equivalent'amount (milligrams) or toxieant for the same eflect r isome, 250) D2 (cyclethrin, 50; n-propyl isome, 250) Values in milligrams are given per 100 millimeters of deodorized kerosene fraction.

The ratio of eifectiveness of the synergized to unsyner- 110 significallfdifiel'eflce in the perfoljmance Q allethlin gized toxicant (allethrin, synergized v. unsynergized; aI 1d cyclethlm when used unsynel'glled agalflst 1101156 cyclethrin, synergized v. unsynergized) based on the forefilesgoing values, are as follows:

EXAMPLE 13 Kill Knockdown Synergized cyclethrin was compared with synergized Synergist allethrm against houseflies m large-group Peet-Grady allethrin oycleallethrin cycletests. The synergists were piperonyl butoxide ((3,4- mm methylenedioxy-G-propyl) benzyl butyl diethylene glycol ether), synergist 6266 (N-hexoxyethoxypropyl) bicyclog gf g gggg g; 1%; 2'? [2.2.1]-5-heptene-2,3-dicarboximide) sulfoxide (n-octyl s .roxid wj 219 1214 119 3Z6 sulfoxide of isosafrole) and n-propyl isome (di-n-propylnPropyhsome- 2 methyl 6,7 methylene dioxy l,2,3,4 hexahydro- Average; 4.1 10. 2 2 7 3.6 naphthalene-3,4-dicairboxylate) Formulation A1 A2 B1 B2 01" 02 D1 D2 allethrin, milligrams 25 30 56 '50 cyclethrin, milligrams- 25 30 60 60 pip eronyl butoxide, milligrams. 200 200 synergist 6266, milli rams 1, 000 I 1,000 sulfoxide, milligrams 250 250 n-propyl isome, milligrams 250 250 deodorized kerosene fraction,

millimeters 100 100 100 100 100 100V 100 100 The results were are the average of four tests are given in the following table:

Percent Percent Formulation 00k- 24 Hours down, 10

Minutes A1 (allethrin plus piperonyl butoxide) 40. 0 90. 0 A2 (cyclethrin plus piperonyl butoxide) 61. 3 91.2 B1 (allethrln plus synergist 6266) 31. 4 92.1 B2 (cyclethrin plus synergist 6266) 46. 6 94. 2 C1 (allethrin plus sulioxide) 37. 2 90. 6 C2 (cyclethrin plus sultoxide) 74. 9 96. 5 D1 (allethrin plus n-propy1,isome) 42. 3 92. 0 D2 (cyclethrin plus n-propyl isome) 63. 4 92. 8

The amountof unsynergized cyclethrin and unsynergized allethrin that would be required to give the same percentkill and knockdown as was obtained above with the synergized material can be estimated by plotting graphicallythe results of Example 12 and taking oif from the curves thus obtained the amounts corresponding to the kills and knockdowns for the synergized material above. The amounts thus estimated are given in the following table:

Tests were conducted on the common housefly using cyclethrin in aerosol formulations according to the official specifications of the Standard'Aerosol Test Method for Flying Insects. Comparison tests werealso carried put using allethrin. Equal .parts of dichlorodifluoromethane (Freon 11) and trichlorofluoromethane (Freon 12) made up parts by weight of each of the formulations. The

Results in Sovaeide 544-0 grams Bayol D Counts of dead larvae were taken after a 72-hour exposure period. Dosage series tests were conducted and Formulation 1 results plotted on log probability paper. terms of percent lethal dose (LD50) were as follows:

Piperonyl Sulfoxide Butoxide Knock down Difference from TOTA Test Percent Referred Oyclethrtn Allethrin DDT Strobane Formulation NOTE-DDT is dichlorodiphenyltrichloroethane; Bayol D is kerosene, highly refined; Strobane is chlorinated hydrocarbon containing percent chlorine, by weight; Sovacide 544%] is aromatic petroleum solvent.

Large group Peer-Grady results Formulation I remaining 15 parts by weight of ingredients making up the formulations were as follows:

1 In addition each formulation contained 10 milliliters of acetone and sufllcient water to make a total volume of 0.1 liter.

The results are set forth in the following table:

Formulation gh H (enethrimn'f 6 gh R (cyclethrin).-. 81 S through U (allethrin) According to the foregoing results, cyclethrin is activated by synergists 264 and 6266 to a greater extent than is allethrin.

EXAMPLE 16 The toxicity to rice weevil was determined for cyclethrin alone and cyclethrin synergized with sulfoxide, piperonyl butoxide and sulfone. For purposes of com- In preparing the formulations,

the active ingredient or active ingredient plus synergist An inert dust, in this case wheat dust, was then added to bring the total weight to The materials were then thoroughly mixed to insure uniformity and the acetone allowed to evapwere kept under fluorescent light at room temperature. orate completely from the mixture. The formulation parison similar tsts were made with allethrin, unsyner- 55 it glligggh D (cyclethrin) P throu gized and synergized.

was dissolved in acetone.

grams.

1 The number of tests carried out on each formulation was five, except 45 U in TOTA-3 and TOTA-4 where ten tests were run. The dosage was the same for eachitest, 31) grams per 1000 cubic feet.

According to the foregoing data obtained with typical aerosol-type formulations, synergized cyclethrin formula- 50 tions are in every instance superior to similar synergized allethrin formulations.

EXAMPLE 15 The efficacy against Mexican bean beetle larvae on tender-green bean was determined for cyclethrin alone and cyclethrin synergized with synergist MGK264,

Similar Preparation of formulations and spraying of plants 65 was done by the method employed in evaluating cyclethrin on bean aphid (Example 11). Two bean plants were used per concentration. After plants had been sprayed and were thoroughly dry, each plant was enclosed in (N-Z-(ethylhexyl) bicyclo 2,2,l-5-heptene-2,3-dicarboximide) and synergist 6266 (N-hexoxyethoxypropyl) bicyclo 2,2,1 5 heptene 2,3 dicarboximide. tests were also run with allethrin and pyrethrins.

a spherical screened cage in which four third inster larvae had been previously placed. Test plants and insects 21 was again thoroughly mixed on a ball mill for one-half hour. The formulations are given in the following table:

22 I butyl ether (viscosity at 100 F.; 250 S.U.S.; average molecular weight about 800) known commercially as Material A B G D E F G H Oyolethrin, milligrams 500 100 100 100 Allethrin, milli ram 500 100 100 100 Piperonyl butoxide, milligrams 1, 600 1, 600 Sulfoxlde, milli rams 1, 600 l, 600 Sulfone, milli ram 1, 600 1, 600 Inert diluent (wheat dust) grams 99. 5 99. 5 98. 3 98. 3 98. 3 98. 3 98. 3 98. 3

The above formulations were placed in four ounce bottles containing two ounces of wheat and the contents mixed by shaking for one-half hour. One hundred adult rice weevils were then introduced into each bottle and allowed to feed for a period of one week. Mortality counts were taken at the end of this exposure. Dosage series tests were run and the results plotted on log probability paper. The results for seven day mortality in terms of lethal dose for 50 percent kill were as follows:

According to the foregoing results, cyclethrin, although only one-third as eifective as allethrin when used alone, is activated or synergized to a greater degree than is allethn'n by the synergists employed. Under actual use conditions, both allethrin and cyclethrin would be used with synergists because of the prohibitive cost of these compounds if used unsynergized. Cyclethrin, because of its freedom from mammalian toxicity, has the advantage that it can beused to protect grain products.

EXAMPLE 17 Another use for cyclethrin indicating its wide range of usefulness is as a larvicide for the control of mosquito larvae. In laboratory tests allethrin and cyclethrin alone, or each with synergist sulfoxide were stirred into 100 milliliters of water containing 20 third instar larvae of the yellow fever mosquito, Aedes aegypli L. Results for the number of dead larvae were taken 48 hours after the larvae were in the water medium. Data shown below indicate the effectiveness of cyclethrin compared with allethrin.

Dosage required for 50 percent Formulation kill (LD-SO) in 48 hrs., parts per million Allethrin; 0. 08 Cyclathrin 0, 07 Allethrin sulfoxide 1 0. 046 Oyclethrln sulfoxide 2 0. 043 Untreated cheeks 1 1 part allethrin parts sufloxide. 2 1 part; eyclethrin 5 parts sulfoxide.

EXAMPLE 18 The synergistic eifect of polyoxypropylene glycol mono Crag fly repellent was tested. The following formulations were preferred:

Formulation A B OTI Cyclethrin, milligrams 84 '84 Allethrin, mi1ligrams. Pyrethrins, milligr 100 Fly repellent, milliliters 10 10 Deodorized kerosene, milliliters..." 9O 90 Large group Peer-Grady test results OTI Difierenco Percent; Percent Formulation N0. of K Knock- Tests 24 Hrs. down, Knock- 10 min. Kill down A. eyclethrin 84 96. 8 +40 +0. 3 B. allethrin. 3 73. 2 98. 1 +29 +1. 6 OT 44.0 96. 5

The results of this test show that the plus value for kill of synergized cyclethrin compared with OTI is better by +11 percentage points than a similar comparison of synergized allethrin; while the knockdown is only slightly less favorable by 1.3 percentage points.

What is claimed is:

1. An insecticidal composition comprising 3-(2-cyclopentenyl) 2 methyl 4 0X0 2 cyclopentenyl chrysanthemumate and a synergist therefor dispersed in an inert diluent; said synergist being selected from the group consisting of piperonyl butoxide, sulfoxide, n-propyl isome, sesame oil, N-(2-ethylheptyl)-bicyclo-[2.2.1l-S- heptene-2,3-dicarboxirnide, N-isobutyl undecylene amide, pinene'ether of ethylene glycol, piperonyl cyclonene, polyoxypropylene glycol monobutyl ether, sulfone; said 3-(2- cyclopentenyl)-2-methyl-4-oxo-2-cyclopentenyl chrysanthemumate being present in the ratio of from 0.0025 to 10 parts for each part of said synergist.

2. An insecticidal composition comprising 3-(2-cyclopentenyl)-2-methyl-4-oxo-2-cyclopentenyl chrysanthemumate and piperonyl butoXide dispersed in an inert diluent, said 3-(2-cyclopentenyl)-2-methy1-4-oXo-2-cyclopentenyl chrysanthemumate being present in the ratio of from 0.0025 to 10 parts for each part of said piperonyl butoxide.

3. An insecticidal composition comprising 3-(2-cyclopentenyl)-2-methyl-4-oXo-2-cyclopentenyl chrysanthemumate and sulfoxide dispersed in an inert diluent, said 3 (2 cyclopentenyl) 2 methyl 4 0X0 2 cyclopentenyl chrysanthemumate being present in the ratio from about 0.0025 to 10 parts for each part of said sulfoxide.

4. An insecticidal composition comprising 3-(2-cyclopentenyl)-2-methyl-4-oxo-2-cyclopentenyl chrysanthemumate and N-(Z-ethylheptyl)-bicyclo-[2.2.1]-5-heptene- 2,3-dicarboximide dispersed in an inert diluent, said 3-(2- cyclopentenyl) 2 methyl 4 oxo 2 cyclopentenyl chrysauthemumate being present in the ratio from about 0.0025 to 10 parts for each part of said N-(2-ethylheptyl) -bicyclo- [2.2. l -5-heptene-2,3,-dicarboximide.

5. An insecticidal composition comprising 3-(2-cyclopentenyl)-2-methyl-4-oxo-2-cyclopentenyl chrysanthemumate and polyoxypropylene glycol monobutyl ether having a viscosity of about 100 to 250 S.U.S. at a temperature of 100 F. and an average molecular weight from about 400 to about 800, dispersed in an inert diluent, said 3-(2-cyclopentenyl) -2-methyl-4-oxo-2-cyclopentenyl chrysanthemumate being present in the ratio from about 0.0025 to 10 parts for each part of said polyoxypropylene glycol monobutyl ether.

6. An insecticidal composition comprising 3-(2-cyclopentenyl -2-methyl-4-oxo-2-cyclopentenyl chrysanthemumate and sulfone dispersed in an inert diluent, said 3 (2 cyclopentyl) 2 methyl 4 oxo 2 cyclo pentenyl chrysanthemumate being present in the ratio from about 0.0025 to 10 parts for each part of said sulfone.

7. An aerosol insecticidal spray composition comprising 3 (2 cyclopentenyl) 2 methyl 4- X0 2- cyclopentenyl chrysanthemumate, a synergist and a propellent, said synergist being of the group consisting of piperonyl butoxide, sulfoxide, n-propyl isome, sesame oil, N (2 ethylheptyl) bicyclo [2.2.1] heptene- 2,3-dicarboximide, N-isobutyl undecylene amide, pinene ether of ethylene glycol, piperonyl cyclonene, polyoxypropylene glycol monobutyl ether, sulfone; said 3-(2-cyclopentenyl) 2 methyl 4 oxo 2 cyclopentenyl chrysanthemumate being present in the ratio from 0.0025 to parts for each part of said synergist.

8. A grain protectant composition comprising 3-(2-cyclopentenyl) 2 methyl 4 oxo 2 cyclopentenyl chrysanthemumate, a synergist therefor and an inert dusttype carrier, said synergist being selected from the group consisting of piperonyl butoxide, sulfoxide, n-propyl isome, sesame oil, N (2 ethylheptyl) bicyclo [2.2.1]- 5 heptene 2,3 dicarboximide, N isobutyl undecylene amide, pinene ether of ethylene glycol, piperonyl cyclonene, polyoxypropylene glycol monobutyl ether, sulfone; said 3 (2 cyclopentenyl) 2 methyl 4 oxo- 2-cyclopentenyl chrysanthemumate being present in the ratio of from 0.0025 to 10 parts for each part of such synergist.

9. A concentrate adapted for mixture with a carrier comprising from 0.1 to 10 parts of 3-(2-cyclopentenyl)-2- methyl4-oxo-2-cyclopentenyl chrysanthemumate to 20 parts of a synergist being selected from the group consisting of piperonyl butoxide, sulfoxide, n-propyl isome, sesame oil, N (2 ethylheptyl) bicyclo [2.2.1] 5- heptene 2,3 dicarboximide, N isobutyl undecylene amide, pinene ether of ethylene glycol, piperonyl cyclonene, polyoxypropylene glycol monobutyl ether, sulfone; said 3 (2 cyclopentenyl) 2 methyl 4 oxo- 2-cyclopentenyl chrysanthemumate being present in the ratio from 0.0025 to 10 parts for each part of such synergist.

10. The method which comprises applying to agricultural and household insects and to their habitats, the composition of claim 1.

11, An aerosol insecticidal spray composition comprising 3 (2 cyclopentenyl) 2 methyl 4 oxo 2- cyclopentenyl chrysanthemumate, a synergist therefor of the group consisting of piperonyl butoxide, sulfoxide, npropyl isome, sesame oil, N (2 ethylheptyl) bicyclo [2.2.1] 5 heptene 2,3 dicarboximide, N-isobutyl undecylene amide, pinene ether of ethylene glycol, piperonyl cyclonene, polyoxypropylene glycol monobutyl ether and sulfone and a chlorofiuoromethane propellent, said 3 (2 cyclopentenyl) 2 methyl 4 0x0 Z-cyclopentenyl chrysanthemumate being present in the ratio of from 0.0025 to 10 parts for each part of said synergist.

12. A concentrate adapted for mixture with a carrier comprising from 0.1 to 10 parts of 3-(2-cyclopentenyl) -2- methyl 4 oxo 2 cyclopentenyl chrysanthemumate to 20 parts of a synergist therefor of the group consisting of piperonyl butoxide, sulfoxide, n-propyl isome, sesame oil, N (2 ethylheptyl) bicyclo [2.2.1] 5 heptene- 2,3-dicarboximide, N-isobutyl undecylene amide, pinene ether of ethylene glycol, piperonyl cyclonene, polyoxypropylene glycol monobutyl ether and sulfone and an emulsifier in an amount not to exceed the amount of syngerist, all by Weight.

13. A concentrate adapted for mixture with a carrier comprising from 0.1 to 10 parts by Weight of 3-(2-cyclopentenyl) 2 methyl 4 oxo 2 cyclopentenyl chrysanthemumate to 20 parts of a synergist therefor of the group consisting of piperonyl butoxide, sulfoxide, n propyl isome, sesame oil, N (2 ethylheptyl) bicyclo [2.2.1] 5 heptene 2,3 dicarboximide, N isobutyl undecylene amide, pinene ether of ethylene glycol, piperonyl cyclonene, polyoxypropylene glycol monobutyl ether and sulfone.

References Cited in the file of this patent UNITED STATES PATENTS Schecter July 15, 1952 Lambrech Nov. 19, 1957 OTHER REFERENCES UNITED STATES PATENT OFFICE Certificate of Correction Patent No. 2,891,889 June 23, 1959 Harry L. Haynes It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction and that the said Letters Patent should read. as corrected below.

Column 3, lines 38 to 41, Step 1, the formula for Q-cyclopeutenyl chloride, should appear as shown below instead of as in the patent:

OH=CH onoi UH -C column 5,,line 7st, for survial read survival--; column 6, line 22, for relate read -related'; column 8 line 12, in the table, first column thereof, for Fly repellent read F1y repellent-; co umn 9, lines 53 and 54, for correponding read corresponding-; column 10, line 58, for Washer read -'Washed-; column 13, line 10, Example 6, in the footnote, line 1, for N- (hyxoxyethoxypropyl) read N- (hexoxyethoxypropy1)- column 15, line 71, in the footnote to the table, for tota read -tota1; column 16, line 7 0, in the table, second column thereof, under the heading LB-50, opposite F through E (allethrin) for 10 read 2-; column 17, Example 12, in the table, first column thereof, under the heading Material, third item, for allthrin read allethrin; same column 17 line 53, for were read -which.

Signed and sealed this 26th day of April 1960.

[SEAL] Attest: KARL H. AXLINE, ROBERT C. WATSON, Attestz'ng Ofiice'r. dommz'ssz'oner of Patents. 

1. AN INSECTICIDAL COMPOSITION COMPRISING 3-(2-CYCLOPENTENYL -2 - METHYL - 4 - OXO - 2 - CYCLOPENTENYL CHRYSANTHEMUMATE AND A SYNERGIST THEREFOR DISPERSED IN AN INERT DILUENT; SAID SYNERGIST BEING SELECTED FROM THE GROUP CONSISTING OF PIPERONYL BUTOXIDE, SULFOXIDE, N-PROPYL ISOME, SESAME OIL, N-(2-ETHYLHEPTYL)-BICYCLO-(2.2.1)-5HEPTENE-2,3-DICARBOXIMIDE, N-ISOBUTYL UNDECYLENE AMIDE PINENE ETHER OF ETHYLENE GLYCOL, PIPERONYL CYCLONENE, POLYOXYPROPYLENE GLYCOL MONOBUTYL ETHER, SULFONE; SAID 3-(2CYCLOPENTENYL)-2-METHYL-4-OXO-2-CYCLOPENTENYL CHRYSANTHEMUMATE BEING PRESENT IN THE RATIO OF FROM 0.0025 TO 10 PARTS FOR EACH PART OF SAID SYNERGIST. 